Chemistry of Heterocyclic Compounds 2020, 56(1), 112–115
1H NMR spectrum, δ, ppm (J, Hz): 4.42 (2H, t, J = 8.0,
NHСН2NH); 6.53 (2Н, s, 2NН); 6.61–6.64 (4H, m, H Ph);
6.89–6.92 (4H, m, H Ph); 8.98 (2Н, s, ОН). 13C NMR
spectrum, δ, ppm: 65.8 (СН2); 116.0 (4C Ph); 120.5 (4C Ph);
139.4 (2CNH Ph); 152.2 (2COH). Found, %: C 67.31;
H 6.30; N 12.38; O 14.01. C13H14N2O2. Calculated, %:
C 67.81; H 6.13; N 12.17; O 13.90.
N,N'-Bis(4-nitrophenyl)methanediamine (3с). Yield
2.19 g (95%), bright-yellow crystals, mp 232°C (decomp.)
(mp 237–239°C16 (decomp.)). IR spectrum, ν, cm–1: 3374
(NH), 3083 (СH), 1604, 1530, 1500, (NO2), 1373 (СN).
1H NMR spectrum, δ, ppm (J, Hz): 4.70 (2H, t, J = 5.8,
NHСН2NH); 6.79 (4H, d, J = 8.0, H Ph); 7.98 (2H, t,
J = 5.8, 2NН); 8.03 (4H, d, J = 8.0, H Ph). 13C NMR spectrum,
δ, ppm: 51.4 (СН2); 112.1 (4C Ph); 126.5 (4C Ph); 137.2
(2СNO2); 153.7 (2СNH Ph). Found, %: C 54.13; H 4.21;
N 19.39; O 22.27. C13H12N4O4. Calculated, %: C 54.17;
H 4.20; N 19.44; O 22.20.
Table 1. The content of THGU (1) dehydroxymethylation
products according to HPLC (n = 3, p = 0.95)
in the synthesis of compound 3d
THGU (1) dehy-
droxymethylation
products
Reaction time,
min
Content
(internal normaliza-
tion), %
1.4
0.5
19.5
40.5
32.2
7.4
8
1.6
5–7
1.8
2.4
4
1
3
Experimental
IR spectra were registered on a FTIR Bruker Alpha
1
spectrometer in KBr in 400–4000 cm–1 range. H and 13C
NMR spectra were acquired on a Bruker Avance III HD
spectrometer (400 and 100 MHz, respectively) in DMSO-d6,
with TMS as internal standard. HPLC was performed on a
chromatograph using a PerfectSil Target ODS-3 HD 5 μ,
250 × 4.6 mm (MZ-Analysentechnik) column thermostatat
temperature of +40°C and 1.5 ml/min flow rate. Run time
10 min, mobile phase H2O, injection volume 10 μl. The
aqueous extract of the reaction mixture of the synthesis of
compound 3d was used for HPLC analysis of compounds
1, 4–8, where product 3d was filtered off, and the filtrate
was used for chromatographic analysis. Elemental analysis
was performed on an Euro Vector EA-3000 CHNS-
analyzer. Melting points were determined on a Buchi
apparatus. Monitoring of the reaction progress and
assessment of the purity of compounds were done by TLC
on Silufol UV-254 plates by disappearance of the
respective amine, eluent PhH–EtOH, 8:2, visualization
with iodine vapors or under UV light (254 nm).
Diethyl 4,4'-(methanediyldiimino)dibenzoate (3d).
Yield 2.68 g (98%), white crystals, mp 190–193°C
(mp 193–194°C17). IR spectrum, ν, cm–1: 3224 (NH), 2980
1
(CH3), 1690 (C=O), 1274 (COC). H NMR spectrum,
δ, ppm (J, Hz): 1.27 (6H, t, J = 7.1, СН3); 4.21 (4H, q,
J = 7.1, СН2СН3); 4.58 (2H, t, J = 5.6, NHСН2NH); 6.74
(4H, d, J = 8.9, H Ph); 7.27 (2H, t, J = 5.8, 2NН); 7.71 (4H,
d, J = 8.9, H Ph). 13C NMR spectrum, δ, ppm: 14.8 (СН3);
51.7 (CH2); 60.1 (CH2); 112.0 (4С Ph); 117.4 (2C-4 Ph);
131.3 (4С Ph); 152.0 (2СNH Ph); 166.3 (C=O). Found, %:
C 66.54; H 6.59; N 8.16; O 18.71. C19H22N2O4. Calculated,
%: C 66.65; H 6.48; N 8.18; O 18.69.
N,N'-Di(quinolin-5-yl)methanediamine (3e). Yield
2.33 g (97%), beige crystals, mp 175°C. IR spectrum, ν, cm–1:
1
3210 (NH), 2926 (CH), 1584 (C=N). H NMR spectrum,
δ, ppm (J, Hz): 4.94 (2H, t, J = 5.2, NHСН2NH); 7.08 (2H,
d, J = 7.8, H Ar); 7.27 (2H, dd, J = 7.8, J = 4.0, Н Ar); 7.27
(2H, t, J = 5.2, 2NН); 7.41 (2H, dd, J = 8.5, J = 4.2, Н Ar);
7.54 (2H, t, J = 8.0, Н Ar); 8.64 (2H, d, J = 8.6, H-4 Ar);
8.77 (2H, dd, J = 4.2, J = 1.4, H-2 Ar). 13C NMR spectrum,
δ, ppm: 53.4 (СН2); 104.7; 117.1; 118.3; 119.6; 130.6;
130.7 (C Ar); 143.8 (CN); 149.2 (CN); 150.3 (CN). Found,
%: C 76.02; H 5.35; N 18.63. C19H16N4. Calculated, %:
C 75.98; H 5.37; N 18.65.
Synthesis of compounds 3a–f (General method).
Aniline 2a–f (0.73 ml, 8 mmol) and tetrakis(hydroxy-
methyl)glycoluril 1 (1.05 g, 4 mmol) were placed in a
100-ml round-bottom flask equipped with a temperature-
resistant stirrer. The mixture was heated to 140–150°C and
stirred until complete conversion of the starting amine and
the mixture becoming turbid due to precipitation (0.5 h).
The mixture was treated with Me2CO, and residual
methylol glycolurils were filtered off. H2O was added
dropwise to the filtrate, and the mixture was kept
overnight. The formed crystals were filtered off, washed
with H2O, and air-dried.
(Diethylamino)ethyl 4,4'-(methanediyldiimino)diben-
zoate (3f). Yield 3.48 g (90%), white crystals, mp 240°C
(decomp.). IR spectrum, ν, cm–1: 3208 (NH), 2981 (CH3),
1
1684 (C=O), 1281 (COC). H NMR spectrum, δ, ppm
(J, Hz): 0.95 (12H, t, J = 8.0, 4NСН2СН3); 2.51 (8H, q,
J = 8.0, 4NСН2СН3); 2.70 (4H, t, J = 6.0, 2СН2N); 4.19
(4H, q, J = 6.0, 2OСН2); 4.57 (2H, t, J = 5.7, NHСН2NH);
6.74 (4H, d, J = 8.8, H Ar); 7.30 (2H, t, J = 5.7, 2NН); 7.69
(4H, d, J = 8.6, H Ar). 13C NMR spectrum, δ, ppm: 12.5
(СН3); 47.5 (CH2СН3); 51.2 (CH2N); 62.7 (NHCH2NH);
65.1 (OCH2); 113.1; 117.3; 131.3 (C Ph), 152.0 (СN Ph);
166.3 (C=O). Found, %: C 66.87; H 8.38; N 11.49;
O 13.26. C27H40N4O4. Calculated, %: C 66.91; H 8.32;
N 11.56; O 13.20.
N,N'-Diphenylmethanediamine (3a). Yield 0.74 g
(94%), white crystals, mp 63°C (mp 64–65°C12).
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IR spectrum, ν, cm–1: 3376 (NH), 2884 (СH2). H NMR
spectrum, δ, ppm: 4.90 (2H, s, NHСН2NH); 6.77–6.80 (2H,
m, H Ph); 6.98–7.02 (2Н, m, 2NН); 7.06–7.08 (4H, m,
H Ph); 7.16–7.20 (4H, m, Ph). 13C NMR spectrum, δ, ppm:
67.4 (СН2); 117.3; 120.3; 129.4; 148.7 (12C Ph). Found,
%: C 78.70; H 7.15; N 14.15. C13H14N2. Calculated, %:
C 78.75; H 7.12; N 14.13.
4,4'-(Methanediyldiimino)diphenol (3b). Yield 0.40 g
(44%), light-beige crystals, mp 230°C (decomp.).
IR spectrum, ν, cm–1: 3194 (NH), 3033–2684 (OH).
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Supplementary information file containing Н and 13С
NMR spectra of all synthesized compounds, as well as
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